Phosphatide product and method of making



cosity reducing power.

Patented {kph-17, 1945 PHOSPHATIDE PRODUCE MAKING AND METHOD Percy L'Julian, Maywood, Edwin W. Meyer, Ev-

anstomand Herbert '1. Iveson, Chicago,- 111,, aasignors, by mesne assignments, to American Lecithin Company, Cleveland, Ohlma corporation Ohio Application July 15, 1942, Serial No. 450,985

8 Claims. (01. 260-403) The present invention relates to the methylation of cephalin and cephalin containing mixtures of phosphatldes.

It is known that phosphatides. such as soybean phosphatides when used in' chocolate in small amounts result in a lowering of the viscosity of the. molten chocolate. Soybean phosphatides consist'essentially of a mixture of, lecithin and cephalin and applicants have observed that when these isolated individual 'phosphatides are used in chocolate that lecithin has a greater viscosity re ducing action than cephalin. As cephalin occurs in. substantial quanities in natural soybean phosphatides as well .as in the 'phosphatides from -other'sources, it is-highlydesirable to increasethe chocolate reducing viscosity of cephalin as wellas mixtures of phosphatides containing cephalin.

It is accordingly an object of the present invention'to treat cephalin and phosphatide mixtures containingcephalin to produce products having.

improved chocolate viscosity reducing power.

Another object is to produce new products from A cephalin which possessv increased chocolate vis- One iormula proposed for lecithin is as follows:

' onion Hon, on- H0 on n\ CHr-O-f|CH z-CH:III QH3 and that for cephalin is 'siippo eateb ammonium compound in which three methyl groups and abasic hydroxyl group are attached to the nitrogen group, and. that cephalin differs therefrom in being a primary amine.

Applicants have found that upon treatment of cephalin with methylating agents that the resulting product produces a greater reductionin the viscosity of chocolate than the untreated ceph-. alin. Lecithin similarly treated does not show any noticeably increased chocolate viscosity reducing power. There are two places where methylation of the cephalin might occur. These are on the acidic hydroxyl group attached to the phosphorus, or on theamino group. Since lecithenitrcgen it would appear that methylation of the cephalin takes place on the amino group.

It is not necessary to treat pure cephalin as mixtures containing cephalin may be treated such as the natural soybean phosphatide mixture.

EXAMPL Crude soybean phosphatides were washed with acetone until oil'freea The oil free phosphatides were then dried and analyzed. A part of the dried phosphatides were then dissolved in refined soya oil to make a mixture containing 70% phosphatides. The oil-phosphatide I mixture was then added to chocolate in various amounts to determine the viscosity reducing action of the resulting mixture. The viscosity'was measured by means of the McMichael viscosimeter. 160

grams of chocolate giving a 3 cm. immersionon a 2 cm. bob were used with a #26 wire at 100 F.

Duplicate runs were made on both the analysis and in the viscosity tests.

10 grams of the oil free soybean phosphatides were dissolved in anhydrous ether and 0.03 mole of diazo-methane in anhydrous ether was added slowly with shaking and the mixture allowed to stand overnight. The ether solution was then vacuum dried and a portion analyzed for nitrogen and .phosphorous. The remainder was then dissolved in soya oil to form a 70% solution and 30 this mixture used in the test for the chocolate viscosity reducing power under the same conditions as above, duplicate runs being made.

To a further 37.5 grams of the oilfree phosphatides was added 12 grams of formic acid a (98%) and 3.3;grams of formaldehyde (37.5%). This mixture was stirred fortwo hours on a steam bath,-'at the end of which time the material was dissolved in hexane, and washed with water containing a small amount of salt to prevent emulsiflcation.- After removal of the excess formic acid and formaldehyde the hexanesolution was concentrated anddried under vacuum. The dried material was analyzed, the remainder dissolved in refined soya oil to a 70% solution mined as above, duplicate runs being made.

The results of the'foregoing experiments are shown in Table I and the 'viscosity reducing actionis further shown graphically in graph No. 1. Averages for the duplicate runs are used.

mixtures against having present any materials which would prevent the'methylation of the cephalin taking place. Thus when cephalin and ceph- 5 5 alin mixtures containing soybean oil are treated and the chocolate viscosity reducing power deter-.

A caution should be observed in treating the reducing power.

graph N013.-

up by reaction with the oil before it has to react with the cephalin.

EXAMPLE II a chance v 2,373,636 v with dlazo meme, the diazo methane is used A study of the table and graphs definitely indicate that methylation ofthe cephalinoccurs,

ably occurs at the amino group.

solved in refined. soybean oil to a 70 solution and the chocolate viscosity reducing power determined, duplicateruns being made. I

Another portion of the soybean lecithin was treated with diazo methane as in Example I,

TABLE I the reaction product analyzed and the viscosity reducing power determined as above.

The alcohol insoluble cephalin fraction left after the alcohol extraction was dissolved in ether and purified by precipitation; in an excess of acetone, and thenin an excess of ethyl alcohol. It

. was then dried and the cephalin thus prepared and tested for chocolate viscosity was analyzed The diazomethane-ce phalin reaction product was then made as previously and the analysis and' hyde duplicate those'with diazo methane, meth- Efiect of methylatzon o phosphattdes Chocolate viscosity- I Analysis McMichael roent Materialadded materials ded Mixed oil-lreesoybean 1.15 3.21 280 171 139 126 131...-

hosphatides.

D zomethane on mixed 1.06 2.99 280 160 119 113 oil-free soybean phos-- phatides.

Formic acid, iormslde- 1.00 2.91 280 168 126 114 118 hyde on mixed oil-free soybfflzlsn phosphatide.

So ybe lecithin 1.60 3.24 280 137 118 109 117 Diazo methane on soy- 1.48 3.24 280 142 114 111 bean lecithin. Soybean cephalln 1.00 3.00 280221 187 175 167-. Diazoln1aeiti1haneonsoybean 0.90 2.96 280 193 157 143 147 cep Formic acid, formalde- 0.85 2.93 280 172 161 137 136 140 yde on soybean cephs- 111. Beeibrainlecithin 1.72 2.93 280 119- 01 99 99 108 Diazomethane on beei- 1.72 2.92 280 117 l 98 99-..-

brain lecithin.

Beeibrain cephalin 1.83 3.27 280 187 149 142 141 143 Diazo methane on beef- 1.80 3.21 280 159 126 v118 brain cephalin.

Fol-mic acid, formaldel.79 ,3.21 280 161 128 110 108 113 hlnde on beefbrain eephchocolate viscosity reducing power run in duplicate.

. The reaction using formic acid and formaldehyde as the methylating agent for the soybean cephaliife was also tried, and the and chocolate viscosity reducing power test made as previously. y 4

The results are shown in the liable I and the viscosity reducing action is further shown graphically in graph No. 2.

EIXAMPLEIII Lecithin'and cephalln were prepared from-beef brains according to the method of Levene, Jr. Biol. Chem. 46 pp. 353-65 (1921) and the same methylated cephalin. i 6. The processwhich comprises reacting the cephalin in a mixture of soybean, phosphatides.

.that lecithin is not methylated and that the methylated cephalin possesses greater chocolate .viscosity reducing power-than the untreated maadvanced the following mechanism tor the re- Since the results with formic acid and formaldeylation must occur and this methylation probably takes. place on the nitrogen atom. This methylation probably does not result in complete conversion to thetertiary amine but it ispossible that some of that product may be produced. However, the invention is not limited by any theory as to the point at which meth'ylation takes place,

The data also show that the results are not specific ror'soybean cephalin and eephalin from any source may be used. Thus cephalins containing' any fatty acid radicals, as well as both alpha and beta cephalins may be employed.

.Also' it is to be understood that the invention is not necessarily limited to the'use of the particular methylating agents employed in the examples but rather that the invention resides' broadly in the methylation of the cephaline by any suitable methylating agent, and to the methylated product.

Having described the invention what is'claimed 1.- As a new compound, methylated cephalin. 2. A composition of matter consisting essentially of methylated soybean cephalin.

3. The process which comprises reacting'cephalin with a methylating agent for cephalin to produce methylated cephalin'."

4. The process which comprises reacting the -cephalin in a mixture of soybean phosphatides with a methylating agent for cephalln toproduce methylated cephalin. v

5. Theprocess which comprises reacting cephalin with a methylating agent selected from the,

class consisting of diazo methane and a mixturev of -tormic acid and iormaldehyde to producewith a methylating agent selected from the class consisting 'of diazo methane ands mixture of .'formic acidand Iormaldehyde to methylate the cephalin in the phosphatide mixture.

7. The process which comprises subjecting an oil-free mixture of soybean phosphatides to the action of diazomethane to methylate the cephalin in the phosphatide mixture.

8. The process which comprises subjecting an oil-free mixture. of s ybean phosphatides to the action .of a mixture of formic acid and formaldehyde to methylate the cephalin' in't/he phos- .bhatide mixture.

tests made as in Example 2.. The results are.

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